JP2011122234A - Plating structure and method for manufacturing electric material - Google Patents

Plating structure and method for manufacturing electric material Download PDF

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JP2011122234A
JP2011122234A JP2010115449A JP2010115449A JP2011122234A JP 2011122234 A JP2011122234 A JP 2011122234A JP 2010115449 A JP2010115449 A JP 2010115449A JP 2010115449 A JP2010115449 A JP 2010115449A JP 2011122234 A JP2011122234 A JP 2011122234A
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plating
silver
tin
light
plated
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JP5612355B2 (en
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Yoshinori Sumitani
義則 墨谷
Kinya Sugie
欣也 杉江
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Kanzacc Co Ltd
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Kyowa Electric Wire Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12681—Ga-, In-, Tl- or Group VA metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Led Device Packages (AREA)
  • Contacts (AREA)
  • Chemically Coating (AREA)
  • Manufacture Of Switches (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a support for storing a light-emitting device therein, which is superior in heat resistance and causes little lowering of reflectivity due to the sulfidizing of silver, and to provide a coating method for an electric component, which is hard to be discolored by sulfidizing, has gloss peculiar to silver and has small contact resistance. <P>SOLUTION: A plating structure is obtained by heat-treating a silver-plated structure which is produced by forming a plated silver layer 104 on the surface of a substrate 102 to be plated, and further forming a plating layer 106 of tin, indium or zinc with a thickness of 0.001-0.1 μm on the surface of the plated silver layer. The coating method includes: forming particle deposits that are arranged so as to have spaces among the deposits without making them overlap in a vertical direction to the surface when viewed from the above, by forming sparsely-deposited particles of tin, indium or zinc, which are deposited like dots on the surface of the silver layer formed on the face of the substrate by a particle deposition process; heating the particle deposits in a non-oxidizing atmosphere; and melting the sparsely-deposited particles to form a coating film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、表面特性の劣化が改善されたメッキ構造、とくには硫化防止を要する電気部品用の材料のメッキ構造、及びそのメッキ構造を有する電気部品用の材料の製造方法に関する。詳しくは、金属リードフレームや金属条を用いたリード線、セラミック等の非導電性基板に設けられたリード線、リードピン、反射板や端子、コネクタ、スイッチなどの電気接点材、として用いて好適な材料のメッキ構造、及びその材料の製造方法に関する。更に詳しくは、耐硫化性に優れる電気部品用材料のメッキ構造及びその製造方法に関する。とくには、本発明は耐硫化性に優れ接触抵抗の低い、あるいは表面の反射率の高い、電気材料のメッキ構造及びその製造方法に関する。 The present invention relates to a plating structure with improved deterioration of surface characteristics, in particular, a plating structure of a material for an electrical component that requires prevention of sulfidation, and a method for manufacturing a material for an electrical component having the plating structure. Specifically, it is suitable for use as a metal lead frame, a lead wire using a metal strip, a lead wire provided on a non-conductive substrate such as a ceramic, an electrical contact material such as a lead pin, a reflector plate, a terminal, a connector, and a switch. The present invention relates to a plated structure of a material and a method for manufacturing the material. More specifically, the present invention relates to a plating structure of a material for electrical parts having excellent resistance to sulfidation and a method for manufacturing the same. In particular, the present invention relates to a plating structure of an electrical material having excellent sulfidation resistance and low contact resistance or high surface reflectance, and a method for producing the same.

ＬＥＤのような発光素子を実装した発光装置は、明るさの向上のため光反射面を設けることが行われる（例えば、特許文献１、２参照）。光反射面は発光素子の側部に放散する光が例えば照射の主軸方向に向くように発光素子の周囲に取り付けられる。光反射面は金属メッキにより形成される。なかでも、銀メッキが高反射のうえで好ましい。   In a light-emitting device in which a light-emitting element such as an LED is mounted, a light reflecting surface is provided to improve brightness (see, for example, Patent Documents 1 and 2). The light reflecting surface is attached to the periphery of the light emitting element so that light radiated to the side of the light emitting element is directed in the direction of the main axis of irradiation, for example. The light reflecting surface is formed by metal plating. Of these, silver plating is preferable because of high reflection.

しかし、銀メッキ層は硫黄が含まれる環境下では、経時や昇温により硫化され反射率が低下するという問題がある。   However, there is a problem in that the silver plating layer is sulfided with time or temperature rise under a sulfur-containing environment, and the reflectance decreases.

このため、反射面に有機物の保護被膜を形成する方策が開示されている。（例えば、特許文献３、４参照）   For this reason, a measure for forming an organic protective film on the reflective surface is disclosed. (For example, see Patent Documents 3 and 4)

あるいは、金属基板上に半フッ化硫黄含有化合物などの物質の自己組織化単分子膜（Self-Assembled Monolayers）を形成して表面を保護する方法が知られている（例えば、特許文献５参照）。   Alternatively, a method for protecting a surface by forming self-assembled monolayers of a substance such as a compound containing sulfur semifluoride on a metal substrate is known (see, for example, Patent Document 5). .

これらの対策はそれなりに有効であるものの、パッケージに樹脂が使用されている場合の実装工程における樹脂のキュアなどによる昇温によって、銀メッキ層の硫化防止のための保護皮膜が飛散して、硫化防止効果が大幅に減少してしまい、反射面の硫化や発光素子の発熱に起因する硫化や装置の長時間使用時の硫化を防止する点では必ずしも満足すべき効果が得られないといえる。この点に鑑みて耐熱性に優れた反射面が望まれている。   Although these measures are effective as they are, the protective film for preventing sulfidation of the silver plating layer scatters due to the temperature rise due to resin curing in the mounting process when resin is used in the package. The prevention effect is greatly reduced, and it can be said that a satisfactory effect is not necessarily obtained in terms of preventing sulfidation due to sulfidation of the reflection surface and heat generation of the light emitting element and sulfidation when the apparatus is used for a long time. In view of this point, a reflecting surface excellent in heat resistance is desired.

さらには、銀メッキ構造がスイッチの接点としても広く用いられる（例えば、特許文献６参照）が、その銀メッキ表面も、経時や、スイッチ製作時のあるいはオンオフ時の放電による昇温により銀メッキ層の硫化防止のための保護皮膜が飛散して、硫化防止効果が大幅に減少してしまい硫化され表面がダメージを受ける場合がある。この点に鑑みて耐熱性に優れたメッキ接点が望まれている。   Furthermore, although a silver plating structure is widely used as a contact point of a switch (see, for example, Patent Document 6), the silver plating surface also has a silver plating layer due to a temperature rise due to discharge over time or during switch production or on / off. In some cases, the protective film for preventing sulfidation is scattered and the effect of preventing sulfidation is greatly reduced, resulting in sulfidation and damage to the surface. In view of this point, a plated contact having excellent heat resistance is desired.

このように、経時や昇温により硫化され表面がダメージを受けることのないメッキ構造が望まれている。   Thus, there is a demand for a plating structure that is sulfided by aging or temperature rise and that does not damage the surface.

また、各種金属基材の表面を銀または銀合金でメッキして耐食性、電気接続性などを改良することが従来から各種の用途で行われており、ＬＥＤでは銀特有の反射性能を生かした反射板として利用されている。   In addition, the surface of various metal substrates is plated with silver or a silver alloy to improve corrosion resistance, electrical connectivity, etc., for a variety of purposes, and LEDs are reflective using the reflective properties peculiar to silver. It is used as a board.

例えば、導電性，熱伝導性に優れ機械的な強度や加工性の点でも優れた銅または銅合金の表面を銀層で被覆した材料は、銅合金の優れた諸特性に加えて、銀の優れた耐食性、電気接続性等も備える材料として知られており、電気機器分野における電気接点材やリードの材料として広く用いられている。   For example, a material in which the surface of copper or copper alloy, which has excellent electrical and thermal conductivity and excellent mechanical strength and workability, is coated with a silver layer, in addition to the excellent characteristics of copper alloy, It is known as a material having excellent corrosion resistance, electrical connectivity, and the like, and is widely used as an electrical contact material and lead material in the field of electrical equipment.

しかし、銀表面は硫化により変色しやすいという問題がある。このため、あるいはまた半田付特性の点から錫または錫合金層を銀表面に形成することが開示されている（例えば、特許文献７参照）。   However, there is a problem that the silver surface is easily discolored by sulfuration. For this reason, or from the viewpoint of soldering characteristics, it is disclosed that a tin or tin alloy layer is formed on the silver surface (see, for example, Patent Document 7).

この場合、錫または錫合金層が厚くなると接触抵抗が増大するという問題が生ずる。また、反射率も低下し銀本来の光沢および反射性能が失われる。   In this case, when the tin or tin alloy layer becomes thick, there arises a problem that the contact resistance increases. In addition, the reflectance is lowered, and the original gloss and reflection performance of silver are lost.

あるいは銀表面に有機薄膜を形成して硫化を防止することも行われるが、有機薄膜は耐熱性に乏しく、高温下での耐硫化性に問題がある。   Alternatively, an organic thin film is formed on the silver surface to prevent sulfidation, but the organic thin film has poor heat resistance and has a problem in sulfidation resistance at high temperatures.

［特許文献１］特開２００８−２０５５０１号公報
［特許文献２］特開２００６−０４１１７９号公報
［特許文献３］特開２００８−０１０５９１号公報
［特許文献４］特開２００３−１８８５０３号公報
［特許文献５］特開２００２−３２７２８３号公報
［特許文献５］特開２００２−３２７２８３号公報
［特許文献６］特開２００８−２４８２９５号公報
[特許文献７] 実公昭６１−１１０８５号公報 [Patent Document 1] JP 2008-205501 [Patent Document 2] JP 2006-041179 [Patent Document 3] JP 2008-010591 [Patent Document 4] JP 2003-188503 [Patent Document 5] Japanese Patent Laid-Open No. 2002-327283 [Patent Document 5] Japanese Patent Laid-Open No. 2002-327283 [Patent Document 6] Japanese Patent Laid-Open No. 2008-248295
[Patent Document 7] Japanese Utility Model Publication No. 61-11085

本発明は、経時や昇温により硫化され表面がダメージを受けることのないメッキ構造を提供することを目的とする。さらには、発光素子を実装した発光装置用の、硫化防止に対する耐熱性に優れたメッキ構造を有する反射面を備える発光素子収納用支持体を提供することを目的とする。   An object of the present invention is to provide a plating structure that is sulfided due to aging or temperature rise and whose surface is not damaged. Furthermore, it aims at providing the support body for light emitting element accommodation provided with the reflective surface which has the plating structure excellent in the heat resistance with respect to sulfidation prevention for the light-emitting devices which mounted the light emitting element.

さらに、本発明の目的は、このようなメッキ構造を有し、硫化により変色しにくく、銀本来の光沢を有し、接触抵抗が小さい電気部品用被覆材を得る電気部品用被覆方法を提供することである。   Furthermore, an object of the present invention is to provide a coating method for electrical parts which has such a plating structure, is not easily discolored by sulfuration, has an original gloss of silver, and has a low contact resistance. That is.

本発明の要旨とするところは、メッキ用基体の表面に銀メッキ層を形成し、さらに該銀メッキ層の表面に厚さ０．００１〜０．１μｍの錫またはインジウムまたは亜鉛のメッキ層を形成してなる銀メッキ構造体を熱処理して得られるメッキ構造であることにある。   The gist of the present invention is that a silver plating layer is formed on the surface of the plating base, and further a tin, indium or zinc plating layer having a thickness of 0.001 to 0.1 μm is formed on the surface of the silver plating layer. The silver-plated structure thus obtained has a plating structure obtained by heat treatment.

また、本発明の要旨とするところは、発光素子収納用の凹部を有し該凹部の周壁で光を反射させる発光素子実装用支持体であって、該凹部の周壁に、該発光素子実装用支持体の本体を前記メッキ用基体として前記メッキ構造が形成された発光素子収納用支持体であることにある。   Further, the gist of the present invention is a light emitting element mounting support that has a concave portion for accommodating a light emitting element and reflects light at the peripheral wall of the concave portion, and the light emitting element mounting support is provided on the peripheral wall of the concave portion. It is a light emitting element housing support in which the plating structure is formed using the main body of the support as the plating base.

さらに、本発明の要旨とするところは、前記発光素子収納用支持体と、該発光素子収納用支持体に実装された発光素子とを含んでなる発光装置であることにある。   Furthermore, the gist of the present invention is a light emitting device including the light emitting element housing support and a light emitting element mounted on the light emitting element housing support.

またさらに、本発明の要旨とするところは、前記メッキ構造を有するメッキ部からなるスイッチ接点であることにある。   Furthermore, the gist of the present invention resides in a switch contact comprising a plated portion having the plated structure.

また、本発明の要旨とするところは、前記メッキ構造を有するメッキ部からなる部品端子であることにある。   Further, the gist of the present invention resides in a component terminal including a plated portion having the plated structure.

さらにまた、本発明の要旨とするところは、前記メッキ構造を有するメッキ部からなる部品接点であることにある。   Furthermore, the gist of the present invention resides in a component contact comprising a plated portion having the plated structure.

また、本発明の要旨とするところは、前記メッキ構造を得る被覆方法であり、
基材の面上に形成された銀層の表面に、粒子堆積工程により点析されてなる錫またはインジウムまたは亜鉛の点析粒子が前記表面と垂直方向に重なることなく上面視で隙間があるように配置され、前記点析粒子の平均径が２０〜８０ｎｍであり、該銀層の表面の錫またはインジウムまたは亜鉛の点析粒子の単位面積当たり重量が２×１０−６〜８×１０−６ｇ／ｃｍ２である粒子堆積物を、非酸化雰囲気で加熱して前記点析粒子を溶融させて被膜化することを特徴とする被覆方法であることにある。 Further, the gist of the present invention is a coating method for obtaining the plating structure,
On the surface of the silver layer formed on the surface of the substrate, tin, indium or zinc diffracted particles splattered by the particle deposition process do not overlap with the surface in the vertical direction so that there is a gap in a top view. The average diameter of the diffracted particles is 20 to 80 nm, and the weight per unit area of the tin, indium or zinc diffracted particles on the surface of the silver layer is 2 × 10 −6 to 8 × 10 −6. It is a coating method characterized in that a particle deposit of g / cm 2 is heated in a non-oxidizing atmosphere to melt the deposited particles to form a film.

本発明によると、経時や特に昇温による硫化防止効果の減少がないメッキ構造が提供される。さらには、発光素子を実装した発光装置用の、耐熱性に優れたメッキ構造を有する反射面を備える発光素子収納用支持体が提供される。   According to the present invention, there is provided a plating structure in which the effect of preventing sulfidation due to aging and particularly temperature rise is not reduced. Furthermore, there is provided a light emitting element storage support including a reflective surface having a plated structure with excellent heat resistance, for a light emitting device on which the light emitting element is mounted.

本発明によると、硫化により変色しにくく、銀本来の光沢を有し、接触抵抗が小さい電気接点材や電気部品用反射材、その他の電気部品用被覆材が提供される。   According to the present invention, there are provided an electrical contact material, a reflective material for electrical components, and other coating materials for electrical components that are difficult to discolor due to sulfuration, have an original gloss of silver, and have low contact resistance.

本発明のメッキ構造を得るための銀メッキ構造体の態様の一例を示す断面説明図である。It is sectional explanatory drawing which shows an example of the aspect of the silver plating structure for obtaining the plating structure of this invention. 本発明のメッキ構造を得るための銀メッキ構造体の他の態様の一例を示す断面説明図である。It is sectional explanatory drawing which shows an example of the other aspect of the silver plating structure for obtaining the plating structure of this invention. 本発明のメッキ構造を有するリードフレームの態様の一例を示す断面説明図である。It is sectional explanatory drawing which shows an example of the aspect of the lead frame which has the plating structure of this invention. 本発明の硫化防止被覆方法により製造される電気部品用被覆材を用いたＬＥＤランプの構成の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of a structure of the LED lamp using the coating | covering material for electrical components manufactured by the sulfurization prevention coating method of this invention. 本発明のメッキ構造を有する試料及び比較試料の反射率のグラフである。It is a graph of the reflectance of the sample which has the plating structure of this invention, and a comparative sample. 本発明に用いられる粒子堆積物の態様を示す断面模式図である。It is a cross-sectional schematic diagram which shows the aspect of the particle deposit used for this invention. 点状に析出した粒子（以下点析粒子と称する）が、互いに隣り合う点析粒子同士が接触した状態すなわち隙間のない状態で面状に配列した粒子堆積物を示す断面模式図である。FIG. 4 is a schematic cross-sectional view showing a particle deposit in which particles deposited in a dot shape (hereinafter referred to as stipulated particles) are arranged in a planar state in a state where stipulated particles adjacent to each other are in contact with each other, that is, without a gap. 互いに隣り合う点析粒子同士が隙間のない状態でかつ、銀層の表面と垂直方向にも重なった状態で立体的に配列した粒子堆積物を示す断面模式図である。It is a cross-sectional schematic diagram which shows the particle | grain deposit arrange | positioned three-dimensionally in the state which the diffracted particle | grains adjacent to each other did not have a clearance gap, and also overlapped with the surface of the silver layer. 本発明の硫化防止被覆方法により製造される電気部品用被覆材の断面模式図である。It is a cross-sectional schematic diagram of the coating | covering material for electrical components manufactured by the sulfide prevention coating method of this invention. 本発明に用いられる粒子堆積物の態様を説明する顕微鏡写真である。It is a microscope picture explaining the aspect of the particle | grain deposit used for this invention. 比較例において用いられる粒子堆積物の態様を説明する顕微鏡写真である。It is a microscope picture explaining the aspect of the particle deposit used in a comparative example.

本発明のメッキ構造は図１（ａ）に示すように、メッキ用基体１０２の表面に銀メッキ層１０４を形成し、さらに銀メッキ層１０４の表面に厚さ０．００１〜０．１μｍの保護メッキ層１０６を形成してなる銀メッキ構造体１０１を１５０〜６００℃で熱処理して得られたメッキ構造である。熱処理時間は1秒〜６０秒が好ましい。   In the plating structure of the present invention, as shown in FIG. 1A, a silver plating layer 104 is formed on the surface of a plating base 102, and a protective layer having a thickness of 0.001 to 0.1 μm is formed on the surface of the silver plating layer 104. This is a plating structure obtained by heat-treating a silver plating structure 101 formed with the plating layer 106 at 150 to 600 ° C. The heat treatment time is preferably 1 second to 60 seconds.

基体１０２は、銀メッキ可能な基体である。基体１０２は金属板からなるものであってもよい。例えば真鍮などの銅系金属、鉄系金属、ステンレスの板が例示されるがこれらに限定されない。なお、通常、銅系金属板を用いた場合はメッキ用基体１０２に銀メッキを施すまえに下地として不図示の銅メッキが施される。ステンレス板を用いた場合はメッキ用基体１０２に銀メッキを施すまえに下地として不図示のニッケルメッキなどが施される。   The base 102 is a base capable of silver plating. The substrate 102 may be made of a metal plate. Examples include, but are not limited to, copper-based metals such as brass, iron-based metals, and stainless steel plates. Usually, when a copper-based metal plate is used, copper plating (not shown) is applied as a base before silver plating is applied to the plating base 102. When a stainless steel plate is used, nickel plating (not shown) is applied as a base before the plating base 102 is silver plated.

あるいは、基体１０２は、セラミックや樹脂をベースとしてその表面に無電解メッキや蒸着や金属層の拡散形成よるメタライズ加工で導電性の皮膜が形成されたものであってもよい。   Alternatively, the substrate 102 may be a substrate in which a conductive film is formed on a surface of ceramic or resin by electroless plating, vapor deposition, or metallization processing by diffusion formation of a metal layer.

基体１０２は図１（ａ）に示すような板状のものに限らず棒状のものであってもよい。すなわち、本発明のメッキ構造は図１（ｂ）に示すように、基体１０２が金属線のような長尺の部材からなり、その周面に銀メッキ層１０４、保護メッキ層１０６がこの順に同心円的に形成されてなる銀メッキ構造体１０１ａを１５０〜６００℃で熱処理して得られたメッキ構造であってもよい。   The substrate 102 is not limited to a plate shape as shown in FIG. That is, in the plating structure of the present invention, as shown in FIG. 1B, the base 102 is made of a long member such as a metal wire, and a silver plating layer 104 and a protective plating layer 106 are concentrically arranged in this order on the peripheral surface. Alternatively, a plated structure obtained by heat-treating the silver-plated structure body 101a formed at 150 to 600 ° C. may be used.

保護メッキ層１０６の厚さは０．００１〜０．１μｍであることが好ましい。保護メッキ層１０６の厚さがこの範囲であると、銀メッキ層１０４の経時や熱による硫化の促進が防止できる。また、メッキ構造が、銀特有の表面特性、例えば良好な光反射性や良好な表面電気電導性や銀特有の光沢を有する。保護メッキ層１０６の厚さがこの範囲を下回ると、この耐硫化性が不十分であり、保護メッキ層１０６の厚さがこの範囲を上回ると、銀特有の表面特性、例えば良好な光反射性や良好な表面電気電導性が得られない。   The thickness of the protective plating layer 106 is preferably 0.001 to 0.1 μm. When the thickness of the protective plating layer 106 is within this range, the silver plating layer 104 can be prevented from being accelerated by aging or heat. Further, the plated structure has surface characteristics peculiar to silver, for example, good light reflectivity, good surface electrical conductivity, and silver peculiar luster. When the thickness of the protective plating layer 106 is less than this range, this resistance to sulfidation is insufficient, and when the thickness of the protective plating layer 106 exceeds this range, surface characteristics peculiar to silver, for example, good light reflectivity. Or good surface conductivity cannot be obtained.

保護メッキ層１０６を構成する金属としては、錫、インジウム、亜鉛が挙げられる。なかでも、錫、インジウムが耐硫化性のうえで好ましい。   Examples of the metal constituting the protective plating layer 106 include tin, indium, and zinc. Of these, tin and indium are preferable in terms of resistance to sulfidation.

本発明のメッキ構造においては、保護メッキ層１０６が上述の加熱による銀メッキ層１０４とマイグレーションにより銀との合金を含むものとなっていてもよい。   In the plated structure of the present invention, the protective plating layer 106 may contain an alloy of silver by migration and the silver plating layer 104 by heating.

銀メッキ層１０４は基体１０２の表面に常法により銀メッキして得ることができる。無電解メッキ等その他の膜形成法によって銀メッキ層１０４が形成されてもよい。銀メッキ層１０４の厚さは０．１〜１０μｍであることが好ましい。銀メッキする基体１０２は表面にニッケル等の下地メッキが施されていることが好ましい。   The silver plating layer 104 can be obtained by silver plating on the surface of the substrate 102 by a conventional method. The silver plating layer 104 may be formed by other film forming methods such as electroless plating. The thickness of the silver plating layer 104 is preferably 0.1 to 10 μm. The base 102 to be silver-plated is preferably provided with a base plating such as nickel on the surface.

銀メッキ構造体１０１は、１５０〜６００℃で熱処理することにより、保護メッキ層１０６の厚さが０．００１〜０．１μｍと薄いにも拘わらず、極めて良好な銀メッキ層１０４の硫化防止効果が得られる。これは、この熱処理により銀メッキ層１０４と保護メッキ層１０６との界面で合金組織が生成し硫化作用に対してガードするためであると推定される。この熱処理温度は２５０〜３００℃であることが硫化防止効果と高い反射率など良好な表面状態を得るうえでさらに好ましい。熱処理の処理時間は1秒〜６０秒であることが好ましい。   The silver plating structure 101 is heat-treated at 150 to 600 ° C., so that the protective plating layer 106 is as thin as 0.001 to 0.1 μm, but the silver plating layer 104 has a very good antisulfurization effect. Is obtained. This is presumed to be due to the fact that an alloy structure is formed at the interface between the silver plating layer 104 and the protective plating layer 106 by this heat treatment and guards against sulfidation. The heat treatment temperature is more preferably 250 to 300 ° C. in order to obtain a good surface state such as an antisulfurization effect and high reflectance. The treatment time for the heat treatment is preferably 1 second to 60 seconds.

この熱処理温度が１５０℃未満であると加熱による錫メッキ層の拡散効果が不十分で充分な硫化防止効果が得られない場合がある。この熱処理温度が６００℃を越えると、基体の焼鈍により基体の物性が変化して実用上必要な基体の機械的特性が損なわれる。   If the heat treatment temperature is less than 150 ° C., the diffusion effect of the tin plating layer by heating may be insufficient and a sufficient antisulfurization effect may not be obtained. If the heat treatment temperature exceeds 600 ° C., the physical properties of the substrate change due to the annealing of the substrate, and the mechanical properties of the substrate necessary for practical use are impaired.

銀メッキ層１０４の厚さは１〜１０μｍであることが好ましい。   The thickness of the silver plating layer 104 is preferably 1 to 10 μm.

銀メッキ層１０４や保護メッキ層１０６は電解メッキや無電解メッキにより形成することができる。   The silver plating layer 104 and the protective plating layer 106 can be formed by electrolytic plating or electroless plating.

本発明のメッキ構造を備えた発光素子収納用支持体の態様の一例を図２に示す。発光素子収納用支持体２０２は、発光素子２０４を収納する凹部２０６を有するリードフレームと称される基板２０３を備えてなる。基板２０３（リードフレーム）はランド２０８とリード２０９から構成され、ランド２０８に凹部２０６が形成されている。発光素子２０４は凹部２０６の底面に載置され発光素子２０４の一方の端子がランド２０８と導通し、他方の端子がワイヤ２１２を介してリード２０９と導通することとなる。   An example of the aspect of the light emitting element accommodation support body provided with the plating structure of the present invention is shown in FIG. The light emitting element storage support 202 includes a substrate 203 called a lead frame having a recess 206 for storing the light emitting element 204. The substrate 203 (lead frame) includes a land 208 and a lead 209, and a recess 206 is formed in the land 208. The light emitting element 204 is placed on the bottom surface of the recess 206, and one terminal of the light emitting element 204 is electrically connected to the land 208, and the other terminal is electrically connected to the lead 209 via the wire 212.

凹部２０６の周面に反射面２１４が形成されている。本発明においては、反射面２１４が、凹部２０６の周面に銀メッキを施したのち、その銀メッキ層の表面にフラッシュメッキなどにより薄い錫メッキ層、インジウムメッキ層あるいは亜鉛メッキ層を形成し、さらに、銀メッキ層の上に薄い錫メッキ層、インジウムメッキ層あるいは亜鉛メッキ層が形成された基板を１５０〜６００℃で熱処理して得られる。   A reflective surface 214 is formed on the peripheral surface of the recess 206. In the present invention, after the reflective surface 214 silver-plats the peripheral surface of the recess 206, a thin tin-plated layer, indium-plated layer or zinc-plated layer is formed on the surface of the silver-plated layer by flash plating or the like, Further, it is obtained by heat-treating a substrate on which a thin tin plating layer, an indium plating layer or a zinc plating layer is formed on a silver plating layer at 150 to 600 ° C.

発光素子２０４としてはＬＥＤが挙げられる。   Examples of the light emitting element 204 include an LED.

図２に示す態様で発光素子２０４が実装されて発光装置が得られる。発光素子２０４の実装工程、たとえば、ケースのモールド、チップとのワイヤボンディング、樹脂のキュアのための加熱により、硫化防止皮膜の飛散による硫化防止効果の減少で、反射面の硫化が促進されることによる反射率の低下が問題となっていた。
発光素子２０４が発光すると発熱がともない、従来の銀メッキ層からなる反射面にあってはこのような発熱による前述と同様の硫化防止効果の減少で硫化が進行する。 A light emitting device is obtained by mounting the light emitting element 204 in the manner shown in FIG. The process of mounting the light emitting element 204, for example, heating of the case mold, wire bonding with the chip, and curing of the resin promotes sulfidation of the reflecting surface by reducing the sulfidation prevention effect due to scattering of the sulfidation prevention film. Decrease in reflectivity due to the problem was a problem.
When the light emitting element 204 emits light, heat is generated, and in the conventional reflective surface made of a silver plating layer, sulfidation proceeds with a decrease in the sulfidation preventing effect similar to that described above.

本発明の発光素子収納用支持体２０２の反射面２１４は経時や反射面の昇温などによる硫化が極めて小さく、長期にわたり高い反射率を維持することができる。   The reflective surface 214 of the light-emitting element storage support 202 of the present invention is extremely low in sulfidation due to aging or temperature rise of the reflective surface, and can maintain a high reflectance over a long period.

図３に本発明による電気部品用被覆材を応用したＬＥＤランプ２０の構造の一例を示す。ＬＥＤランプ２０においては、ＬＥＤ ２６が基盤２２上に載置され、ケーシング２４に収められている。ケーシング２４の中にはＬＥＤ ２６が蛍光体２８に埋没した状態で蛍光体２８が充填され、さらに蛍光体２８の上面に透明樹脂カバー３０が設けられている。符号３４はリード線である。基盤２２の本体基材としては銅合金等の金属部材あるいはメタライズ加工されたセラミック部材が用いられ、その表面に本発明による銀メッキと錫またはインジウムメッキが施された反射面３２が形成されている。反射面３２が銀面なみの反射性を有し、かつ経時による硫化に起因する変色がほとんどないので、ＬＥＤランプ２０は出射光量が大きくかつ経時による出射光量の低下が少ない。   FIG. 3 shows an example of the structure of the LED lamp 20 to which the coating material for electric parts according to the present invention is applied. In the LED lamp 20, the LED 26 is placed on the base 22 and stored in the casing 24. The casing 24 is filled with the phosphor 28 with the LED 26 embedded in the phosphor 28, and a transparent resin cover 30 is provided on the upper surface of the phosphor 28. Reference numeral 34 denotes a lead wire. A metal member such as a copper alloy or a metallized ceramic member is used as the main body of the substrate 22, and a reflective surface 32 is formed on the surface of which the silver plating and tin or indium plating according to the present invention is applied. . Since the reflecting surface 32 has reflectivity similar to that of a silver surface and there is almost no discoloration due to sulfidation over time, the LED lamp 20 has a large amount of emitted light and a small decrease in the amount of emitted light over time.

本発明のメッキ構造はスイッチ接点に適用することができる。本発明のメッキ構造を有するスイッチ接点は、銀特有の光沢と良好な表面電気電導性を有し、長期の使用によっても硫化によるこれら表面特性の変化が少ない。例えば、リードフレームに素子をマウントし、ボンディング／樹脂成型し、メッキ後にプレス加工してスイッチ接点等に組み立てられる。   The plating structure of the present invention can be applied to switch contacts. The switch contact having the plated structure of the present invention has a gloss unique to silver and good surface electrical conductivity, and the surface characteristics are hardly changed by sulfidation even when used for a long time. For example, an element is mounted on a lead frame, bonded / resin-molded, pressed after plating, and assembled into a switch contact or the like.

本発明のメッキ構造は電気機器の接点や端子に適用することができる。本発明のメッキ構造を有する接点や端子は、銀特有の光沢と良好な表面電気電導性を有し、長期の使用によっても硫化によるこれら表面特性の変化が少ない。   The plating structure of the present invention can be applied to contacts and terminals of electrical equipment. The contacts and terminals having the plated structure of the present invention have a gloss unique to silver and good surface electrical conductivity, and even when used for a long time, these surface characteristics are hardly changed by sulfidation.

本発明の効果は以下に示す実験例により確認される。   The effect of the present invention is confirmed by the following experimental examples.

［実験例］ [Experimental example]

・基本試料
図１のメッキ用基体１０２に相当するものとして、リードフレーム用銅合金条（古河電工社製：品名ＥＦＴＥＣ３）の１ｃｍ角のピースを用いた。このピースの片面に１μｍの銅の下地メッキを施したのち、厚さ２μｍの銀メッキを施して基本試料とし、この基本試料に以下の各実験水準に応じて錫メッキと熱処理などを行った。 Basic Sample A 1 cm square piece of copper alloy strip for lead frame (manufactured by Furukawa Electric Co., Ltd .: product name EFTEC3) was used as the equivalent of the plating base 102 in FIG. After applying 1 μm copper underplating to one side of this piece, 2 μm thick silver plating was used as a basic sample, and this basic sample was subjected to tin plating and heat treatment according to the following experimental levels.

・実験試料水準
Ｌ−１：ブランク（基本試料のまま）
Ｌ−２：基本試料の銀面にフラッシュメッキにより厚さ０．０１μｍの錫層を形成した。
Ｌ−３：基本試料の銀面にフラッシュメッキにより厚さ０．０１μｍの錫層を形成したのち、試料を３００℃で１０秒間熱処理した。
Ｌ−４：基本試料の銀面にフラッシュメッキにより厚さ０．０２μｍの錫層を形成した。
Ｌ−５：基本試料の銀面にフラッシュメッキにより厚さ０．０２μｍの錫層を形成したのち、試料を３００℃１０秒間熱処理した。
Ｌ−６：基本試料の銀面にフラッシュメッキにより厚さ０．２μｍの錫層を形成した。
Ｌ−７：基本試料の銀面に自己組織化単分子膜を形成する硫化防止剤を用いて硫化防止を目的とする有機被膜を形成した。
表１に実験試料水準とその内容の一覧表を示す。 ・ Experimental sample level L-1: Blank (as basic sample)
L-2: A tin layer having a thickness of 0.01 μm was formed on the silver surface of the basic sample by flash plating.
L-3: A tin layer having a thickness of 0.01 μm was formed by flash plating on the silver surface of the basic sample, and then the sample was heat-treated at 300 ° C. for 10 seconds.
L-4: A 0.02 μm thick tin layer was formed on the silver surface of the basic sample by flash plating.
L-5: After forming a 0.02 μm thick tin layer on the silver surface of the basic sample by flash plating, the sample was heat-treated at 300 ° C. for 10 seconds.
L-6: A tin layer having a thickness of 0.2 μm was formed on the silver surface of the basic sample by flash plating.
L-7: An organic film intended to prevent sulfidation was formed using a sulfidation inhibitor that forms a self-assembled monolayer on the silver surface of the basic sample.
Table 1 shows a list of experimental sample levels and their contents.

・硫化テスト
硫化アンモニウム６重量％溶液２０ｍＬに水４００ｃｃを加えた浸漬液に試料を５分間室温で浸漬することにより硫化処理した。浸漬完了後のピースを純水洗浄後メタノール置換し、窒素流でブローし、その後試料を各温度（表１）で１時間加熱して硫化を促進させた。硫化の程度は目視判定した。この硫化処理誤の加熱は長期間にわたる硫化作用の加速試験に対応する。また、機器の組み立て時や使用時における昇温にも対応する。 -Sulfide test A sample was immersed in an immersion solution obtained by adding 400 cc of water to 20 mL of a 6% by weight ammonium sulfide solution, and the sample was subjected to sulfurization treatment at room temperature for 5 minutes. The piece after completion of the immersion was washed with pure water and then replaced with methanol, and blown with a nitrogen flow, and then the sample was heated at each temperature (Table 1) for 1 hour to promote sulfidation. The degree of sulfuration was judged visually. This erroneous heating of sulfidation corresponds to an accelerated test of sulfidation over a long period of time. It also supports temperature rise during device assembly and use.

・判定基準は
◎・・・銀表面の光沢、色調が維持されている（硫化処理前）。または、表面に硫化が認められず銀表面の光沢、色調が維持されている（硫化処理後）。
○・・・銀表面の光沢、色調がほぼ維持されている（硫化処理前）。または表面に硫化がほとんど認められず銀表面の光沢、色調がほぼ維持されている（硫化処理後）。
△・・・銀表面の光沢、色調が容認できる程度に維持されている（硫化処理前）。または、表面に硫化がやや認められるが銀表面の光沢、色調が容認できる程度に維持されている（硫化処理後）。
×・・・銀表面の光沢、色調が失われている（硫化処理前）。または、表面に硫化が認められ銀表面の光沢、色調が失われている（硫化処理後）。
とした。 ・ Judgment criteria are ◎ ・ ・ ・ Gloss and tone of the silver surface are maintained (before sulfidation). Alternatively, no sulfidation is observed on the surface, and the gloss and color tone of the silver surface are maintained (after sulfidation treatment).
○: The gloss and color tone of the silver surface are almost maintained (before sulfurization treatment). Alternatively, the surface is hardly sulphurized, and the gloss and color tone of the silver surface are almost maintained (after sulphurizing treatment).
Δ: The gloss and color tone of the silver surface are maintained to an acceptable level (before sulfurization treatment). Alternatively, although some sulfuration is observed on the surface, the gloss and color tone of the silver surface are maintained to an acceptable level (after sulfuration treatment).
X: The gloss and color tone of the silver surface are lost (before sulfurization treatment). Alternatively, sulfuration is observed on the surface, and the glossiness and color tone of the silver surface are lost (after sulfuration treatment).
It was.

・反射率
実験試料の硫化テスト前後の反射率をＪＩＳ Ｒ３１０６に準拠してＤ６５光源での波長範囲３８０〜７８０ｎｍの光によって測定した。 -Reflectance The reflectance of the experimental sample before and after the sulfidation test was measured with light having a wavelength range of 380 to 780 nm with a D65 light source in accordance with JIS R3106.

Figure 2011122234
Figure 2011122234

・テスト結果
硫化テストの結果を表２に示す。 Test results Table 2 shows the results of the sulfidation test.

Figure 2011122234
Figure 2011122234

表２より、錫層の厚さが０．０１μｍのもの（Ｌ−２、Ｌ−３）は硫化処理前には銀表面の光沢、色調が維持されていることがわかる。また、錫層の厚さが０．０２μｍのもの（Ｌ−４、Ｌ−５）は硫化処理前には銀表面の光沢、色調がほぼ維持される。さらに、錫層を形成したのち、試料を３００℃１０秒間熱処理したもの（Ｌ−３）は、錫層の厚さが０．０１μｍとごく薄いにも拘わらず硫化処理後の加熱によっても表面に硫化がほとんど認められず銀表面の光沢、色調がほぼ維持されている。錫層を形成したのち、熱処理しないもの（Ｌ−２、Ｌ−４）については、錫層の厚さが０．０１μｍとごく薄いもの（Ｌ−２）は、硫化処理後の高温加熱によって表面が硫化されて銀表面の光沢、色調が失われる。錫層の厚さが０．０２μｍのもの（Ｌ−４）は、錫層を形成したのちの熱処理がなくとも、硫化処理後の加熱によって硫化される度合いが比較的小さい。錫層の厚さが０．２μｍのもの（Ｌ−６）は硫化処理前であっても錫層によるマスクのため銀表面の光沢、色調が失われている。基本試料の銀面に有機被膜を形成したもの（Ｌ−７）は硫化処理により表面が硫化されて銀表面の光沢、色調が失われる。   From Table 2, it can be seen that when the tin layer has a thickness of 0.01 μm (L-2, L-3), the gloss and color tone of the silver surface are maintained before the sulfiding treatment. Further, when the tin layer has a thickness of 0.02 μm (L-4, L-5), the gloss and color tone of the silver surface are substantially maintained before the sulfiding treatment. Further, after the tin layer was formed, the sample (L-3), which was heat-treated at 300 ° C. for 10 seconds, was applied to the surface by heating after the sulfiding treatment even though the thickness of the tin layer was as thin as 0.01 μm. There is almost no sulfidation, and the gloss and color tone of the silver surface are almost maintained. After forming the tin layer, those that are not heat-treated (L-2, L-4) are those whose tin layer is as thin as 0.01 μm (L-2). Is sulfidized, and the gloss and color tone of the silver surface is lost. In the case where the thickness of the tin layer is 0.02 μm (L-4), the degree of sulfidation by the heating after the sulfiding treatment is relatively small even without the heat treatment after the tin layer is formed. When the tin layer has a thickness of 0.2 μm (L-6), the luster and color tone of the silver surface are lost because of the mask with the tin layer even before the sulfidation treatment. In the basic sample having an organic film formed on the silver surface (L-7), the surface is sulfided by sulfidation, and the gloss and color tone of the silver surface are lost.

図４に反射率の測定結果を示す。試料として実験試料Ｌ−３、Ｌ−７を用い、
イ．実験試料Ｌ−３
ロ．実験試料Ｌ−３を硫化処理したもの
ハ．実験試料Ｌ−３を硫化処理後１８０℃１時間加熱したもの
ニ．実験試料Ｌ−７を硫化処理後１８０℃１時間加熱したもの
の４種類について反射率を測定した。 FIG. 4 shows the measurement results of the reflectance. Experimental samples L-3 and L-7 were used as samples,
I. Experimental sample L-3
B. A sample obtained by subjecting experimental sample L-3 to sulfuration c. Experimental sample L-3 heated at 180 ° C. for 1 hour after sulfiding The reflectance was measured for four types of experimental samples L-7 heated at 180 ° C. for 1 hour after sulfiding.

図４より、基本試料の銀面に有機被膜を形成したもの（Ｌ−７）は硫化処理により反射率が著しく低下する（ニ）ことがわかる。厚さ０．０１μｍの錫層を形成したのち、試料を３００℃１０秒間熱処理したもの（Ｌ−３）は、波長４５０ｎｍにおいて反射率は９３％、また、可視光のほとんどすべての波長域で８０％以上と良好な反射率を有し、硫化処理によっても反射率の低下は少なく、硫化処理後の反射率は従来品であるＬ−７の硫化処理後の反射率よりもはるかに高く、例えば、ニ．の波長４５０ｎｍにおける反射率は６７％であるのに対して、（ロ）は波長４５０ｎｍにおいて９０％であった。さらに、Ｌ−３を硫化処理後１８０℃１時間加熱したもの（ハ）についても、反射率の低下は少なく、例えば波長４５０ｎｍにおいて８５％であった。   FIG. 4 shows that the reflectance of the basic sample with the organic film formed on the silver surface (L-7) is remarkably lowered by the sulfidation treatment (d). After forming a tin layer having a thickness of 0.01 μm and heat-treating the sample at 300 ° C. for 10 seconds (L-3), the reflectance is 93% at a wavelength of 450 nm, and 80% in almost all the wavelength range of visible light. %, The reflectance after the sulfiding treatment is much lower than the reflectance after the sulfiding treatment of the conventional product L-7, for example, , D. The reflectance at a wavelength of 450 nm was 67%, while (b) was 90% at a wavelength of 450 nm. Furthermore, L-3 was heated at 180 ° C. for 1 hour after being subjected to sulfurization treatment (c), and the reflectivity was little decreased, for example, 85% at a wavelength of 450 nm.

本発明のメッキ構造を得るための被覆方法による電気部品用被覆材の製造の態様の一例においては、まず、銀メッキ層１０４（図１）が形成された基体１０２を準備し、その銀メッキ層１０４の表面に粒子堆積工程により錫粒子またはインジウム粒子または亜鉛粒子を堆積させる。このとき、図５に示すように、粒子堆積工程により微小塊状に析出した点析粒子８の少なくとも一部が銀メッキ層１０４の表面に、互いに隣り合う点析粒子８の間に隙間１０が存在して面状にまばらに位置するように、かつ、銀メッキ層１０４の表面と垂直方向に重なることなく配されるように短時間の通電を行う。面状にまばらに位置するとは銀メッキ層１０４の表面にメッキ等の粒子堆積工程によりにより錫またはインジウム粒子または亜鉛粒子を堆積させたある所定の領域について、上面視で見える銀メッキ層１０４の面積がその領域全体の面積の１５％以上である状態をいう。この上面視で見える銀メッキ層１０４の面積は前記の領域全体の面積の１５〜５０％であることが好ましい。この値が５０％を上回ると本発明において均一な薄膜７が得られない。   In an example of an aspect of manufacturing a coating material for electrical parts by a coating method for obtaining a plating structure of the present invention, first, a base 102 on which a silver plating layer 104 (FIG. 1) is formed is prepared, and the silver plating layer is prepared. Tin particles, indium particles, or zinc particles are deposited on the surface of 104 by a particle deposition process. At this time, as shown in FIG. 5, at least a part of the splattered particles 8 deposited in the form of fine lumps by the particle deposition step is present on the surface of the silver plating layer 104, and there is a gap 10 between the stipulated particles 8 adjacent to each other. Then, the energization is performed for a short time so as to be sparsely arranged in a plane shape and arranged so as not to overlap the surface of the silver plating layer 104 in the vertical direction. The sparsely located area means the area of the silver plating layer 104 that can be seen in a top view with respect to a predetermined region where tin, indium particles, or zinc particles are deposited on the surface of the silver plating layer 104 by a particle deposition process such as plating. Is a state in which the area is 15% or more of the entire area. The area of the silver plating layer 104 that can be seen from above is preferably 15 to 50% of the area of the entire region. If this value exceeds 50%, a uniform thin film 7 cannot be obtained in the present invention.

本発明における粒子堆積工程は、化学的手段、電気的手段、物理的手段から選択される手段により、基板上に目的とする金属粒子を堆積させる工程であり、具体的には電気メッキ法、無電解メッキ法、真空蒸着法、化学的蒸着法、スパッタ法、プラズマ堆積法、クラスターイオンビーム法などを用いた工程が挙げられる。なかでも電気メッキ法が製造コストを低くできる点で好ましい。   The particle deposition step in the present invention is a step of depositing target metal particles on a substrate by means selected from chemical means, electrical means, and physical means. Examples include a process using an electrolytic plating method, a vacuum deposition method, a chemical vapor deposition method, a sputtering method, a plasma deposition method, a cluster ion beam method, and the like. Among these, the electroplating method is preferable in that the manufacturing cost can be reduced.

例えば、粒子堆積工程として電気メッキ工程を用いた場合、通電時間が長くなると図６に示すように、点析粒子８が、互いに隣り合う点析粒子８同士が接触した状態すなわち隙間のない状態で面状に配列する。あるいは、図７に示すように、互いに隣り合う点析粒子８同士が隙間のない状態でかつ、銀メッキ層１０４の表面と垂直方向にも重なった状態で立体的に配列する。   For example, when an electroplating process is used as the particle deposition process, as the energization time becomes longer, as shown in FIG. 6, the splattered particles 8 are in contact with each other adjacent to each other, that is, without a gap. Arrange in a plane. Alternatively, as shown in FIG. 7, the stipulated particles 8 adjacent to each other are arranged in a three-dimensional manner in a state where there is no gap and also in the direction perpendicular to the surface of the silver plating layer 104.

例えば、粒子堆積工程として電気メッキ工程を用いた場合、図５に示すような互いに隣り合う点析粒子８の間に隙間１０が存在して面状にまばらに位置する状態を得るためには、通電時間は１〜１２０秒の範囲で選択されることが好ましい。かつ、メッキ液の錫またはインジウムまたは亜鉛成分濃度を通常のメッキの条件より小さく、例えば通常のメッキ液（例えば、メタスルホン酸錫５０〜１００ｇ／Ｌ）の濃度の１／５〜１／２０に調整することが好ましい。   For example, when an electroplating process is used as the particle deposition process, in order to obtain a state in which gaps 10 exist between the adjacent splatting particles 8 as shown in FIG. The energization time is preferably selected in the range of 1 to 120 seconds. In addition, the tin, indium or zinc component concentration of the plating solution is smaller than the normal plating conditions, for example, adjusted to 1/5 to 1/20 of the concentration of a normal plating solution (for example, tin metasulfonate 50-100 g / L). It is preferable to do.

点析粒子８の粒子径は２０〜８０ｎｍであることが本発明において電気部品用被覆材の均一な被膜を得るうえで好ましい。３０〜６０ｎｍであることが電気部品用被覆材の良好な反射性と硫化防止性のバランスが最適化されるうえでさらに好ましい。例えば、通常の錫メッキ浴についてその錫成分濃度を１／５〜１／２０に調整したメッキ浴を用い、通電の電流密度を０．５〜１０Ａ／ｄｍ２の範囲で選択することによりこのような粒子径の点析粒子８が得られる。この場合、通電時間はメッキ液の濃度により調整する。あるいは、例えば、マイクロセコンドオーダーのパルス通電を行うことにより２０〜３０ｎｍに近い範囲の粒子径の点析粒子８が得られる。 In the present invention, the particle diameter of the diffracted particles 8 is preferably 20 to 80 nm in order to obtain a uniform film of the coating material for electric parts. A thickness of 30 to 60 nm is more preferable in optimizing the balance between good reflectivity and antisulfurization property of the coating material for electric parts. For example, by using a plating bath in which the tin component concentration is adjusted to 1/5 to 1/20 with respect to a normal tin plating bath, the current density of energization is selected in the range of 0.5 to 10 A / dm 2. Thus, diffracted particles 8 having a proper particle diameter are obtained. In this case, the energization time is adjusted by the concentration of the plating solution. Alternatively, for example, pulverized particles 8 having a particle diameter in a range close to 20 to 30 nm can be obtained by performing microsecond order pulse energization.

本発明においては、図５に示すような、粒子堆積工程により点析されてなる錫またはインジウムまたは亜鉛の点析粒子８が銀メッキ層１０４の表面と垂直方向に実質的に重なることなくかつ点析粒子８の少なくとも一部が互いに間隔をおいてまばらに位置された粒子堆積物１２を非酸化雰囲気で加熱して錫またはインジウムまたは亜鉛の点析粒子８を溶融させて被膜化する。非酸化雰囲気は錫またはインジウムまたは亜鉛がたかだか無視できる程度にしか酸化されない雰囲気であり、この非酸化雰囲気での加熱としては、窒素等の不活性気体中での加熱、真空中での加熱、還元炎による加熱などが挙げられる。加熱温度は堆積された金属（錫またはインジウムまたは亜鉛）の融点以上、６００℃以下であることが好ましい。   In the present invention, as shown in FIG. 5, the diffracted particles 8 of tin, indium, or zinc formed by the particle deposition step do not substantially overlap the surface of the silver plating layer 104 in the vertical direction. The particle deposit 12 in which at least some of the deposited particles 8 are sparsely spaced apart from each other is heated in a non-oxidizing atmosphere to melt the deposited particles 8 of tin, indium or zinc to form a film. A non-oxidizing atmosphere is an atmosphere in which tin, indium or zinc is oxidized to a negligible extent. Heating in this non-oxidizing atmosphere includes heating in an inert gas such as nitrogen, heating in a vacuum, and reduction. For example, heating by flame. The heating temperature is preferably not lower than the melting point of the deposited metal (tin, indium or zinc) and not higher than 600 ° C.

これにより、図８に示すような、基体１０２の表面に銀メッキ層１０４が形成され、さらに銀メッキ層１０４の表面に錫または錫合金の薄膜７、あるいはインジウムまたはインジウム合金、あるいは亜鉛または亜鉛合金の薄膜７が形成されてなる電気部品用被覆材２２２が形成される。   As a result, a silver plating layer 104 is formed on the surface of the substrate 102 as shown in FIG. 8, and a thin film 7 of tin or tin alloy, or indium or indium alloy, or zinc or zinc alloy is further formed on the surface of the silver plating layer 104. An electrical component covering material 222 formed by forming the thin film 7 is formed.

粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量は２×１０−６〜８×１０−６ｇ／ｃｍ２であることが好ましい。この値は、点析粒子８が溶融固化して銀メッキ層１０４の表面で錫からなる薄膜となったと仮定した場合のその錫からなる薄膜の厚さが約３〜１１ｎｍとなる点析粒子８の単位面積当たり重量に相当する。例えば錫を用いた場合、実際には薄膜７は錫及び／又は銀と錫の合金からなると推定され、例えば、粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量が３×１０−６であるときの薄膜７の厚さは銀、錫の熱拡散層を含んで４ｎｍ以上であると推定され、粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量が８×１０−６であるときの薄膜７の厚さは１１ｎｍ以上であると推定される。いずれにしても、薄膜７に存在する単位面積当たりの錫またはインジウムの重量は、粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量と同じである。 The weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 is preferably 2 × 10 −6 to 8 × 10 −6 g / cm 2 . This value is based on the assumption that the thickness of the thin film made of tin is about 3 to 11 nm when it is assumed that the thinned film 8 is melted and solidified to form a thin film made of tin on the surface of the silver plating layer 104. It corresponds to the weight per unit area. For example, when tin is used, the thin film 7 is actually assumed to be made of tin and / or an alloy of silver and tin. For example, the weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 When the thickness of the thin film 7 is 3 × 10 −6 , the thickness of the thin film 7 is estimated to be 4 nm or more including the thermal diffusion layer of silver and tin, and the scattered particles 8 on the surface of the silver plating layer 104 in the particle deposit 12. The thickness of the thin film 7 when the weight per unit area is 8 × 10 −6 is estimated to be 11 nm or more. In any case, the weight of tin or indium per unit area existing in the thin film 7 is the same as the weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12.

粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量が５×１０−６〜７×１０−６ｇ／ｃｍ２であることが、接触抵抗、銀光沢、耐硫化性のバランスのうえでさらに好ましい。 The weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 is 5 × 10 −6 to 7 × 10 −6 g / cm 2 , so that contact resistance, silver luster, and sulfuration resistance More preferable in terms of balance of sex.

薄膜７に存在する単位面積当たりの錫またはインジウムまたは亜鉛の量や、粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量は、蛍光Ｘ線分析装置により測定することができる。   The amount of tin, indium or zinc per unit area existing in the thin film 7 and the weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 should be measured with a fluorescent X-ray analyzer. Can do.

かかる本発明の電気部品用被覆材の製造方法により得られた電気部品用被覆材は、硫化しにくくかつ接触抵抗が銀に近く、銀特有の光沢を備える。錫とインジウムと亜鉛を比較すると、本発明においてインジウムを用いた電気部品用被覆材のほうが、錫を用いた電気部品用被覆材より硫化しにくくより好ましい。錫を用いた電気部品用被覆材のほうが亜鉛を用いた電気部品用被覆材より硫化しにくくより好ましい   The electrical component coating material obtained by the method for producing an electrical component coating material of the present invention is less susceptible to sulfidation, has a contact resistance close to silver, and has a gloss characteristic of silver. When tin, indium and zinc are compared, in the present invention, the coating material for electrical parts using indium is more preferable than the coating material for electrical parts using tin, which is less susceptible to sulfidation. The coating material for electric parts using tin is more preferable than the coating material for electric parts using zinc.

粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量が２×１０−６ｇ／ｃｍ２を下回ると得られた電気部品用被覆材の硫化防止性能が劣る。粒子堆積物１２における銀メッキ層１０４の表面の点析粒子８の単位面積当たり重量が１１×１０−６ｇ／ｃｍ２を上回ると得られた電気部品用被覆材の接触抵抗が過大となり、銀特有の光沢が失われる。また、錫またはインジウムまたは亜鉛の点析粒子８が銀メッキ層１０４の表面に互いに隣り合う点析粒子８がほとんどすべて接触する状態（これを隙間のない状態という）で配された状態の粒子堆積物を用いた場合は加熱による所望の厚さの均一な薄膜形成が難しく、得られた電気部品用被覆材の接触抵抗が過大となり、銀特有の光沢が失われる。隙間のない状態はある一の点析粒子を面状に囲む複数の点析粒子のうちの少なくとも４個の点析粒子がこの一の点析粒子と接触している状態をいう。また、銀メッキ層１０４の表面に点析粒子を粒子堆積工程により堆積させたある所定の領域について、上面視で見える銀メッキ層１０４の面積がその領域全体の面積の１５％を下回ると加熱による所望の厚さの均一な薄膜形成が難しく、得られた電気部品用被覆材の接触抵抗が過大となり、銀特有の光沢が失われる。 When the weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 is less than 2 × 10 −6 g / cm 2 , the sulfidation prevention performance of the obtained coating material for electrical parts is inferior. When the weight per unit area of the diffracted particles 8 on the surface of the silver plating layer 104 in the particle deposit 12 exceeds 11 × 10 −6 g / cm 2 , the contact resistance of the obtained coating material for electrical parts becomes excessive, and silver The characteristic luster is lost. In addition, particle deposition in a state in which diffracted particles 8 of tin, indium, or zinc are arranged in a state where almost all of the diffracted particles 8 adjacent to each other are in contact with the surface of the silver plating layer 104 (this is referred to as a state having no gap). When an object is used, it is difficult to form a uniform thin film with a desired thickness by heating, the contact resistance of the obtained coating material for electric parts becomes excessive, and silver-specific luster is lost. The state without a gap refers to a state in which at least four of the diffracted particles surrounding a certain diffracted particle in a plane are in contact with the one diffracted particle. In addition, when a predetermined area where diffracted particles are deposited on the surface of the silver plating layer 104 by the particle deposition process, the area of the silver plating layer 104 seen from the top view is less than 15% of the total area, the heating It is difficult to form a uniform thin film having a desired thickness, the contact resistance of the obtained coating material for electrical parts is excessive, and the silver specific luster is lost.

また点析粒子８が銀メッキ層１０４の表面と垂直方向に重なった状態で配された粒子堆積物を用いた場合も加熱による所望の厚さの均一な薄膜形成が難しく、得られた電気部品用被覆材の接触抵抗が過大となり、銀特有の光沢が失われる。   In addition, when a particle deposit in which the diffracted particles 8 are arranged in a state where the diffracted particles 8 overlap with the surface of the silver plating layer 104 is used, it is difficult to form a uniform thin film having a desired thickness by heating. The contact resistance of the coating material becomes excessive, and the gloss peculiar to silver is lost.

また、粒子堆積物１２を酸化雰囲気で加熱した場合は、錫またはインジウムまたは亜鉛は酸化すると流動性が低下するため、点析粒子８の均一な被膜化がなされず、均一な薄膜７が得られない。   In addition, when the particle deposit 12 is heated in an oxidizing atmosphere, the fluidity is lowered when tin, indium or zinc is oxidized, so that the diffracted particles 8 are not uniformly coated, and a uniform thin film 7 is obtained. Absent.

［実施例１］
図２に示す基板２０３の形状のフレームに銀メッキと錫メッキを施した。基体としてのフレームの材料としては、リードフレーム用銅合金条（古河電工社製：ＥＦＴＥＣ３）を用い、打ち抜き加工により成形した。フレームを脱脂処理後５％硫酸で酸洗浄し、光沢硫酸銅浴（硫酸銅２００ｇ／／Ｌ、硫酸５０ｇ／／Ｌ、市販光沢剤２ｍＬ／／Ｌ）で下地銅メッキした。下地銅メッキの膜厚は１．０μｍであった。次いで、光沢シアン化銀浴（シアン化銀３５ｇ／／Ｌ、シアン化カリウム９０ｇ／／Ｌ、炭酸カリウム１０ｇ／／Ｌ）で膜厚２μｍの光沢銀メッキを行った。さらに、アルカノールスルホン浴（第一錫１８ｇ／／Ｌ、遊離酸１００ｇ／／Ｌ、半光沢剤１０ｍＬ／／Ｌ）で膜厚０．０１μｍの錫メッキを施したのち、２５０℃で１０秒間熱処理してリードフレームを得た。硫化テストを行ない、表１のＬ−３と同様の結果が得られた。 [Example 1]
Silver plating and tin plating were applied to the frame having the shape of the substrate 203 shown in FIG. As a material of the frame as a base, a copper alloy strip for lead frame (Furukawa Electric Co., Ltd .: EFTEC3) was used and molded by punching. The frame was degreased, acid washed with 5% sulfuric acid, and plated with a base copper in a bright copper sulfate bath (copper sulfate 200 g // L, sulfuric acid 50 g // L, commercially available brightener 2 mL // L). The film thickness of the base copper plating was 1.0 μm. Next, bright silver plating with a film thickness of 2 μm was performed in a bright silver cyanide bath (silver cyanide 35 g // L, potassium cyanide 90 g // L, potassium carbonate 10 g // L). Furthermore, after tin plating with a film thickness of 0.01 μm was performed in an alkanol sulfone bath (stannous 18 g // L, free acid 100 g // L, semi-brightening agent 10 mL // L), heat treatment was performed at 250 ° C. for 10 seconds. I got a lead frame. A sulfurization test was performed, and the same result as L-3 in Table 1 was obtained.

［実施例２］
厚さ１ｍｍ、１ｃｍ角のステンレス（ＳＵＳ３０４）板を基体とし、脱脂処理後５％硫酸で酸洗浄し、光沢硫酸銅浴（硫酸銅２００ｇ／／Ｌ、硫酸５０ｇ／／Ｌ、市販光沢剤２ｍＬ／／Ｌ）で下地銅メッキした。下地銅メッキの膜厚は１．０μｍであった。次いで、光沢シアン化銀浴（シアン化銀３５ｇ／／Ｌ、シアン化カリウム９０ｇ／／Ｌ、炭酸カリウム１０ｇ／／Ｌ）で膜厚２μｍの光沢銀メッキを行った。さらに、アルカノールスルホン浴（第一錫１８ｇ／／Ｌ、遊離酸１００ｇ／／Ｌ、半光沢剤１０ｍＬ／／Ｌ）で膜厚０．０１μｍの錫メッキを施したのち、５００℃で１０秒間熱処理して光沢板を得た。硫化テストを行ない、表１のＬ−３と同様の結果が得られた。 [Example 2]
A stainless steel (SUS304) plate with a thickness of 1 mm and 1 cm square is used as a base. After degreasing, it is acid-washed with 5% sulfuric acid, and a bright copper sulfate bath (copper sulfate 200 g // L, sulfuric acid 50 g // L, commercially available brightener 2 mL / / L). The film thickness of the base copper plating was 1.0 μm. Next, bright silver plating with a film thickness of 2 μm was performed in a bright silver cyanide bath (silver cyanide 35 g // L, potassium cyanide 90 g // L, potassium carbonate 10 g // L). Furthermore, after tin plating with a film thickness of 0.01 μm was performed in an alkanol sulfone bath (stannous 18 g // L, free acid 100 g // L, semi-brightening agent 10 mL // L), heat treatment was performed at 500 ° C. for 10 seconds. A glossy plate was obtained. A sulfurization test was performed, and the same result as L-3 in Table 1 was obtained.

［比較例１］
錫メッキを施したのちの熱処理温度を１００℃とした以外は実施例１と同様にしてリードフレームを得た。硫化テストを行ない、表１のＬ−２と同様の結果が得られた。 [Comparative Example 1]
A lead frame was obtained in the same manner as in Example 1 except that the heat treatment temperature after tin plating was set to 100 ° C. A sulfurization test was performed, and the same result as L-2 in Table 1 was obtained.

[実施例３]
厚さ０．３ｍｍの真鍮製条材に０．５μｍのニッケル下地メッキを行ったものを基板とした。その基板の表面に厚さ２μｍの銀メッキを施し、基礎試料とした。 [Example 3]
A substrate obtained by subjecting a brass strip with a thickness of 0.3 mm to a nickel base plating of 0.5 μm was used. The surface of the substrate was subjected to silver plating with a thickness of 2 μm to obtain a basic sample.

基礎試料に下記条件で錫メッキを施し粒子堆積物を得た。
メッキ液組成 メタスルホン酸：１００ｇ／Ｌ
メタスルホン酸錫：５ｇ／Ｌ
界面活性剤：３ｇ／Ｌ
メッキ温度 ４２℃
電流密度 ２Ａ／ｄｍ２
通電時間 ４秒 The basic sample was subjected to tin plating under the following conditions to obtain a particle deposit.
Plating solution composition Metasulfonic acid: 100 g / L
Tin metasulfonate: 5 g / L
Surfactant: 3g / L
Plating temperature 42 ℃
Current density 2A / dm 2
Energizing time 4 seconds

得られた粒子堆積物は、図９に示すものと同じように、基礎試料の表面に錫の点析粒子８がその表面と垂直方向に重なることなくかつ上面視で隙間１０があるように配置された状態であった。点析粒子８の平均径は５０ｎｍであった。また、粒子堆積物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による錫の量は５×１０−６ｇ／ｃｍ２であった。 As in the case shown in FIG. 9, the obtained particle deposit is arranged so that the tin diffracted particles 8 do not overlap the surface of the basic sample in the direction perpendicular to the surface and there is a gap 10 in a top view. It was a state that was done. The average diameter of the diffracted particles 8 was 50 nm. Moreover, the quantity of the tin by the fluorescent X-ray-analysis apparatus (made by SSI nanotechnology company) of a particle deposit was 5 * 10 < -6 > g / cm < 2 >.

この粒子堆積物をバーナーを用いて／ＬPガスの還元炎中で１０秒間加熱し、電気部品用被覆材を得た。ガスの燃焼雰囲気温度は３５０℃であった。   This particle deposit was heated in a reducing flame of LP gas using a burner for 10 seconds to obtain a coating material for electric parts. The gas combustion atmosphere temperature was 350 ° C.

[実施例４]
実施例３で用いたと同様の基礎試料に下記条件で錫メッキを施し粒子堆積物を得た。
メッキ液組成 実施例３と同じ
メッキ温度 実施例３と同じ
電流密度 平均１０Ａ／ｄｍ２
通電時間 １０秒（パルス通電：周期１００μｓｅｃ） [Example 4]
The same basic sample as used in Example 3 was tin-plated under the following conditions to obtain a particle deposit.
Plating solution composition Same as Example 3 Plating temperature Same as Example 3 Current density 10 A / dm 2 on average
Energization time 10 seconds (pulse energization: period 100 μsec)

得られた粒子堆積物は、基礎試料の表面に錫の点析粒子８がその表面と垂直方向に重なることなくかつ間隔をおいて配置された状態である。点析粒子８の平均径は３０ｎｍであった。また、粒子堆積物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による錫の量は３×１０−６ｇ／ｃｍ２であった。 The obtained particle deposit is in a state in which the tin diffracted particles 8 are arranged on the surface of the basic sample without being overlapped in the direction perpendicular to the surface. The average diameter of the diffracted particles 8 was 30 nm. Moreover, the quantity of the tin by the fluorescent X-ray-analysis apparatus (made by SSI nanotechnology company) of a particle deposit was 3 * 10 < -6 > g / cm < 2 >.

この粒子堆積物を実施例３と同様にして加熱し、電気部品用被覆材を得た   This particle deposit was heated in the same manner as in Example 3 to obtain a coating material for electrical parts.

[実施例５]
実施例３で用いたと同様の基礎試料に下記条件で錫メッキを施し粒子堆積物を得た。
メッキ液組成 実施例３と同じ
メッキ温度 実施例３と同じ
電流密度 １０Ａ／ｄｍ２
通電時間 ６秒
得られた粒子堆積物は、基礎試料の表面に錫の点析粒子８がその表面と垂直方向に重なることなくかつ間隔をおいて配置された状態である。点析粒子８の平均径は５０ｎｍであった。また、粒子堆積物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による錫の量は７．３×１０−６ｇ／ｃｍ２であった。
この粒子堆積物を実施例３と同様にして加熱し、電気部品用被覆材を得た [Example 5]
The same basic sample as used in Example 3 was tin-plated under the following conditions to obtain a particle deposit.
Plating solution composition Same as Example 3 Plating temperature Same as Example 3 Current density 10 A / dm 2
Energization time: 6 seconds The obtained particle deposit is in a state in which the tin diffracted particles 8 are arranged on the surface of the basic sample without overlapping with the surface in the direction perpendicular to the surface. The average diameter of the diffracted particles 8 was 50 nm. Moreover, the quantity of the tin by the fluorescent X-ray-analysis apparatus (made by SSI nanotechnology company) of a particle deposit was 7.3 * 10 < -6 > g / cm < 2 >.
This particle deposit was heated in the same manner as in Example 3 to obtain a coating material for electrical parts.

[実施例６]
実施例３で用いたと同様の基礎試料に下記条件でインジウムめっきを施しメッキ物を得た。
メッキ液組成 スルファミン酸インジウム：１００ｇ／L
界面活性剤：８００ｍＬ／L
メッキ液温度 ３０℃
電流密度 ２Ａ／ｄｍ２
通電時間 6秒 [Example 6]
The same basic sample as used in Example 3 was subjected to indium plating under the following conditions to obtain a plated product.
Plating solution composition Indium sulfamate: 100 g / L
Surfactant: 800mL / L
Plating solution temperature 30 ℃
Current density 2A / dm 2
Energizing time 6 seconds

得られたメッキ物は、基礎試料の表面にインジウムの点析粒子８がその表面と垂直方向に重なることなくかつ上面視で隙間があるように配置された状態であった。点析粒子８の平均径は５０ｎｍであった。また、メッキ物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）によるインジウムの量は７．３×１０−６ｇ／ｃｍ２であった。 The obtained plated product was in a state in which the indium diffracted particles 8 were arranged on the surface of the basic sample so as not to overlap with the surface in a vertical direction and with a gap in a top view. The average diameter of the diffracted particles 8 was 50 nm. Moreover, the amount of indium by a fluorescent X-ray analyzer (made by SSI Nanotechnology Co., Ltd.) for the plated product was 7.3 × 10 −6 g / cm 2 .

このメッキ物をバーナーを用いて／ＬPガスの250℃還元炎中で１０秒間加熱し、電気部品用メッキ材を得た。   This plated product was heated for 10 seconds in a 250 ° C. reducing flame of LP gas using a burner to obtain a plating material for electric parts.

[実施例７]
実施例３で用いたと同様の基礎試料に下記条件で亜鉛めっきを施しメッキ物を得た。
メッキ液組成 酸化亜鉛：５g／L
苛性ソーダ：１００ｇ／L
添加剤：１０ｇ／L
メッキ液温度 ３０℃
電流密度 ２Ａ／ｄｍ２
通電時間 ５秒 [Example 7]
The same basic sample as used in Example 3 was galvanized under the following conditions to obtain a plated product.
Plating solution composition Zinc oxide: 5g / L
Caustic soda: 100 g / L
Additive: 10g / L
Plating solution temperature 30 ℃
Current density 2A / dm 2
Energizing time 5 seconds

得られたメッキ物は、基礎試料の表面に亜鉛の点析粒子８がその表面と垂直方向に重なることなくかつ上面視で隙間があるように配置された状態であった。点析粒子８の平均径は５０ｎｍであった。また、メッキ物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による亜鉛の量は７．１×１０−６ｇ／ｃｍ２であった。 The obtained plated product was in a state in which the zinc diffracted particles 8 were arranged on the surface of the basic sample so as not to overlap with the surface in a vertical direction and with a gap in a top view. The average diameter of the diffracted particles 8 was 50 nm. Moreover, the amount of zinc by a fluorescent X-ray analyzer (made by SSI Nanotechnology Co., Ltd.) of the plated product was 7.1 × 10 −6 g / cm 2 .

このメッキ物をバーナーを用いて／ＬPガスの５００℃還元炎中で１０秒間加熱し、電気部品用メッキ材を得た。   This plated product was heated in a 500 ° C. reducing flame of / LP gas using a burner for 10 seconds to obtain a plating material for electric parts.

［比較例２］
実施例３で用いたと同様の基礎試料に下記条件で錫メッキを施し粒子堆積物を得た。
メッキ液組成 実施例３と同じ
メッキ温度 実施例３と同じ
電流密度 １０Ａ／ｄｍ２
通電時間 １．５秒
得られた粒子堆積物は、基礎試料の表面に錫の点析粒子８がその表面と垂直方向に重なることなくかつ間隔をおいて配置された状態である。点析粒子８の平均径は３０ｎｍであった。また、粒子堆積物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による錫の量は１．９×１０−６ｇ／ｃｍ２であった。
この粒子堆積物を実施例３と同様にして加熱し、電気部品用被覆材を得た [Comparative Example 2]
The same basic sample as used in Example 3 was tin-plated under the following conditions to obtain a particle deposit.
Plating solution composition Same as Example 3 Plating temperature Same as Example 3 Current density 10 A / dm 2
Energization time 1.5 seconds The obtained particle deposit is in a state in which the tin diffracted particles 8 are arranged on the surface of the basic sample without being overlapped in the direction perpendicular to the surface. The average diameter of the diffracted particles 8 was 30 nm. Moreover, the quantity of the tin by the fluorescent X-ray-analysis apparatus (made by SSI nanotechnology company) of a particle deposit was 1.9 * 10 < -6 > g / cm < 2 >.
This particle deposit was heated in the same manner as in Example 3 to obtain a coating material for electrical parts.

［比較例３］
実施例３で用いたと同様の基礎試料に下記条件で錫メッキを施し粒子堆積物を得た。
メッキ液組成 メタスルホン酸：１００ｇ／Ｌ
メタスルホン酸錫：実施例３の１０倍当量／Ｌ
界面活性剤：３０ｇ／Ｌ
メッキ温度 ４２℃
電流密度 ２Ａ／ｄｍ２
通電時間 ４秒 [Comparative Example 3]
The same basic sample as used in Example 3 was tin-plated under the following conditions to obtain a particle deposit.
Plating solution composition Metasulfonic acid: 100 g / L
Tin metasulfonate: 10 times equivalent / L of Example 3
Surfactant: 30 g / L
Plating temperature 42 ℃
Current density 2A / dm 2
Energizing time 4 seconds

得られた粒子堆積物は、図１０に示すものと同じように基礎試料の表面に錫の点析粒子８がその表面と垂直方向に一部重なりかつ間隔をおかず互いに隣り合う点析粒子が接触した配置された状態である。点析粒子８の平均径は１００ｎｍであった。また、粒子堆積物の蛍光Ｘ線分析装置（エスエスアイ・ナノテクノロジー社製）による錫の量は５×１０−５ｇ／ｃｍ２であった。 The obtained particle deposit is similar to the one shown in FIG. 10, where the tin diffracted particles 8 partially overlap the surface of the basic sample in the direction perpendicular to the surface, and the adjacent diffracted particles are in contact with each other. It is the state that was arranged. The average diameter of the diffracted particles 8 was 100 nm. Moreover, the quantity of the tin by the fluorescent X-ray-analysis apparatus (made by SSI nanotechnology company) of a particle deposit was 5 * 10 < -5 > g / cm < 2 >.

この粒子堆積物を実施例３と同様にして加熱し、電気部品用被覆材を得た   This particle deposit was heated in the same manner as in Example 3 to obtain a coating material for electrical parts.

基礎試料及び実施例、比較例で得られた電気部品用被覆材の特性を表３に示す。表中耐硫化性は、試料の電気部品用被覆材を２００℃で１時間加熱した後、濃度６重量％の硫化アンモニウム溶液に常温で１０分間浸漬後、純水洗浄してメタノール置換し、窒素流でブローしたときの変色の度合いであり、◎◎：変色が認められない ◎：変色がほとんど認められない○：わずかに変色が認められるが許容範囲である △：変色が認められるが許容範囲である ×：著しい変色が認められる を表す。また、接触抵抗（ｍΩ）は、交流４端子法により、プローブの材質をＮＳ／Ａｕ、先端形状を１．０Ｒとし、測定電流を１００μＡ、荷重３０ｇｆで測定した。反射率は、Ｕ−４０００形分光光度計で測定した波長４５０ｎｍの反射率である。   Table 3 shows the characteristics of the covering materials for electrical parts obtained in the basic sample, the examples, and the comparative examples. In the table, the resistance to sulfidation is as follows: the sample coating material for electric parts was heated at 200 ° C. for 1 hour, then immersed in an ammonium sulfide solution having a concentration of 6% by weight at room temperature for 10 minutes, washed with pure water, and replaced with methanol. Degree of discoloration when blown in a flow, ◎: No discoloration ◎: Almost no discoloration ○: Slight discoloration is acceptable but acceptable △: Discoloration is acceptable but acceptable X: Remarkable discoloration is observed. The contact resistance (mΩ) was measured by an alternating current four-terminal method with a probe material of NS / Au, a tip shape of 1.0 R, a measurement current of 100 μA, and a load of 30 gf. The reflectance is a reflectance at a wavelength of 450 nm measured with a U-4000 type spectrophotometer.

Figure 2011122234
Figure 2011122234

本発明は、銀の高反射特性や、高表面電気電導特性等の表面特性を利用した各種の機器における銀表面の硫化防止に好適に適当される。とくには、光学機械、スイッチ、部品接点、部品端子、真空断熱材、などに好適に適用できる。
本発明により得られる電気部品用被覆材は、接触抵抗が低く、耐硫化性に優れ、銀本来の光沢を有するので、端子，コネクタ，スイッチなどの電気接点材のみならず、ＩＣパッケージのリード線やリードピン、またはリードフレームなどのリード材料、ＬＥＤランプ等照明具用の反射材、燃料電池用の導電材料、等電気（電子）材料として好適に用いることができる。 The present invention is suitably suitable for preventing sulfidation of the silver surface in various devices utilizing surface characteristics such as high reflection characteristics and high surface electrical conductivity characteristics of silver. In particular, it can be suitably applied to optical machines, switches, component contacts, component terminals, vacuum heat insulating materials, and the like.
The coating material for electrical parts obtained by the present invention has low contact resistance, excellent sulfidation resistance, and has the original gloss of silver. Therefore, not only electrical contact materials such as terminals, connectors and switches, but also lead wires for IC packages And lead materials such as lead pins or lead frames, reflectors for lighting fixtures such as LED lamps, conductive materials for fuel cells, and other electrical (electronic) materials.

７：薄膜
８：点析粒子
１０：隙間
１０１、１０１ａ：銀メッキ構造体
１０２：メッキ用基体
１０４：銀メッキ層
１０６：保護メッキ層
２２２：電気部品用被覆材 7: Thin film 8: Dotted particles 10: Crevice 101, 101a: Silver plating structure 102: Plating substrate 104: Silver plating layer 106: Protective plating layer 222: Coating material for electric parts

Claims (7)

メッキ用基体の表面に銀メッキ層を形成し、さらに該銀メッキ層の表面に厚さ０．００１〜０．１μｍの錫またはインジウムまたは亜鉛のメッキ層を形成してなる銀メッキ構造体を熱処理して得られるメッキ構造。 A silver plating structure is formed by forming a silver plating layer on the surface of the plating base, and further forming a 0.001 to 0.1 μm thick tin, indium or zinc plating layer on the surface of the silver plating layer. Plating structure obtained in this way. 発光素子収納用の凹部を有し該凹部の周壁で光を反射させる発光素子実装用支持体であって、該凹部の周壁に、該発光素子実装用支持体の本体を前記メッキ用基体として請求項１に記載のメッキ構造が形成された発光素子収納用支持体。 A light-emitting element mounting support having a recess for housing a light-emitting element and reflecting light at the peripheral wall of the recess, wherein the main body of the light-emitting element mounting support is claimed as the plating base on the peripheral wall of the recess Item 8. A light-emitting element storage support on which the plating structure according to Item 1 is formed. 請求項２に記載の発光素子収納用支持体と、該発光素子収納用支持体に実装された発光素子とを含んでなる発光装置。 A light-emitting device comprising the light-emitting element storage support according to claim 2 and a light-emitting element mounted on the light-emitting element storage support. 請求項１に記載のメッキ構造を有するメッキ部からなるスイッチ接点。 The switch contact which consists of a plating part which has the plating structure of Claim 1. 請求項１に記載のメッキ構造を有するメッキ部からなる部品端子。 The component terminal which consists of a plating part which has the plating structure of Claim 1. 請求項１に記載のメッキ構造を有するメッキ部からなる部品接点。 A component contact comprising a plated portion having the plated structure according to claim 1. 請求項１に記載のメッキ構造を得る被覆方法であり、
基材の面上に形成された銀層の表面に、粒子堆積工程により点析されてなる錫またはインジウムまたは亜鉛の点析粒子が前記表面と垂直方向に重なることなく上面視で隙間があるように配置され、前記点析粒子の平均径が２０〜８０ｎｍであり、該銀層の表面の錫またはインジウムまたは亜鉛の点析粒子の単位面積当たり重量が２×１０−６〜８×１０−６ｇ／ｃｍ２である粒子堆積物を、非酸化雰囲気で加熱して前記点析粒子を溶融させて被膜化することを特徴とする被覆方法。 A coating method for obtaining the plated structure according to claim 1,
On the surface of the silver layer formed on the surface of the substrate, tin, indium or zinc diffracted particles splattered by the particle deposition process do not overlap with the surface in the vertical direction so that there is a gap in a top view. The average diameter of the diffracted particles is 20 to 80 nm, and the weight per unit area of the tin, indium or zinc diffracted particles on the surface of the silver layer is 2 × 10 −6 to 8 × 10 −6. A coating method comprising heating a particle deposit of g / cm 2 in a non-oxidizing atmosphere to melt the deposited particles to form a film.
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